CN108048876A - Dedicated hematite iron of aluminium electrolysis anode and preparation method and application - Google Patents
Dedicated hematite iron of aluminium electrolysis anode and preparation method and application Download PDFInfo
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- CN108048876A CN108048876A CN201711259981.1A CN201711259981A CN108048876A CN 108048876 A CN108048876 A CN 108048876A CN 201711259981 A CN201711259981 A CN 201711259981A CN 108048876 A CN108048876 A CN 108048876A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/08—Making cast-iron alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/10—Cast-iron alloys containing aluminium or silicon
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Abstract
The present invention relates to dedicated hematite irons of a kind of aluminium electrolysis anode and preparation method and application, and in hematite iron, the mass percentage of phosphorus is 0.15%；The mass percentage of carbon is 2.3%~3.34%；The mass percentage of silicon is 3.0%~3.7%；The mass percentage of manganese is less than 0.8%；The mass percentage of sulphur is 0.051%~0.2%.The present invention is by the way that silicone content is heightened, phosphorus content is turned down, and the iron carbon pressure drop for the hematite iron being prepared can be controlled in optimum range, and the indication range pressure drop that average pressure drop can be than in the prior art reduces by 25~30mV, by taking 100,000 tons of electrolytic aluminiums as an example, power consumption cost 3,200,000 or so can be saved；And because phosphorus content is relatively low, when ensureing the mobility and brittleness of molten iron, can enter to avoid phosphorus element sulphur in cell bath reduces the adverse effect of electrolytic cell currents efficiency, so as to reduce the risk of P elements pollution.
Description
Technical field
The present invention relates to electrochemical technology fields, and in particular to a kind of dedicated hematite iron of aluminium electrolysis anode and its preparation
Method and application.
Background technology
In aluminium anodes module production process, hematite iron plays the role of contacting carbon and carbon bowl steel pawl, hematite iron
The content of middle carbon silicomanganese phosphorus sulphur, it will influence the iron hoop energy after the pressure drop and return between the quality containing hematite iron, iron carbon
No pressure-off is fallen.The influence of each element is as follows：
1) carbon influences the intensity of casting, hardness and ductility.It can increase casting by adjusting carbon element content
Mobility and heat conduction/electric conductivity；
2) element silicon can enhance the degree of graphitization of casting and the mobility of molten iron, weaken iron blockage effect；
3) manganese element can interfere casting to be graphitized and can form manganese sulfide, have certain desulfidation, while can also carry
The intensity of high cast iron can also enhance iron blockage effect；
4) P elements can make casting generate cold short phenomenon, weaken iron blockage effect, enhance the mobility of molten iron, but increasing
During subtracting P elements, electrolyte enters inside electric slot the current efficiency that will influence electrolytic cell；
5) element sulphur is harmful to casting, and ring decrepitation can be generated containing element sulphur in casting, reduces cold draw under high temperature
Property, shrinkage cavity defect is generated, increases iron carbon pressure drop.
In traditional phosphorus pig iron production process, the contents of five big elemental carbon silicon of molten iron is usually than relatively low, and phosphorus contains
Amount is higher, and increases the content of phosphorus in iron by adding in substantial amounts of ferrophosphorus and other materials into raw material, so as to protect
The mobility and cold brittleness of molten iron are demonstrate,proved, but P elements can be caused to be flowed into electrolyte, this can cause the electric current of electrolytic cell to be imitated
Rate reduces, and phosphorus element content will not reduce in electrolyte in use, while seriously pollute molten aluminum and electrolyte.
The content of the invention
For in the prior art the defects of, present invention aims at provide a kind of dedicated hematite iron of aluminium electrolysis anode and
Its preparation method and application, with by the way that silicone content is heightened, phosphorus content is turned down, the iron carbon pressure drop for the hematite iron being prepared can
To control in optimum range, average pressure drop can than in the prior art indication range pressure drop of the prior art be reduced to 25~
30mV by taking 100,000 tons of electrolytic aluminiums as an example, can save power consumption cost 3,200,000 or so every year；And because phosphorus content is relatively low, ensureing
When the mobility and brittleness of molten iron, can enter to avoid phosphorus element sulphur in cell bath reduces electrolytic cell currents efficiency not
Profit influences, so as to reduce the risk of P elements pollution.
To achieve the above object, technical solution provided by the invention is：
In a first aspect, the present invention provides a kind of dedicated hematite iron of aluminium electrolysis anode, in hematite iron, the quality of phosphorus
Percentage composition is 0.15%.
Preferably, in hematite iron：The mass percentage of carbon is 2.3%~3.34%；The mass percentage of silicon is
3.0%~3.7%；The mass percentage of manganese is less than 0.8%；The mass percentage of sulphur is 0.051%~0.2%.
Preferably, in hematite iron：The mass percentage of nickel element is 0.1%~1.0%；The quality hundred of rare earth element
It is 0.3%~0.5% to divide content.
It should be noted that the mass percentage optimum value of carbon is 3.2%, mass percentage highest does not allow more than
3.34%；Because being learnt through overtesting, if the mass percentage of carbon is more than 3.35%, iron hoop intensity increases, the coefficient of expansion
Increase, the surface of iron hoop is present with bulge phenomenon, seriously affects the casting quality of iron hoop.
The mass percentage optimum value of silicon is 3.2%, and the mass percentage of element silicon does not allow less than 3.0%, because
It is element silicon in addition to it can promote graphited effect, the mobility of molten iron can also be improved, one is played in molten iron
The effect of deoxidation, if percentage amounts containing quality are less than 3.0%, the Ferropho hours ring pressure-disengaging of return is difficult, and it is serious while tight that guide rod is stained with iron
Ghost image rings the mobility of molten iron.
The mass percentage optimum value of manganese be 0.35%, manganese element can improve the hardness of cast iron, in molten iron except
Play the role of a desulfurization, while can be very good the dilatancy of comprehensive carbon, manganese is element indispensable in cast iron, still
Must reasonably control it there are ratios.
The mass percentage optimum value of phosphorus is 0.15%, and phosphorus can improve the mobility and cold brittleness of molten iron, but it
To exist to drastically influence electrical efficiency in anode iron hoop, at the same be also influence iron carbon pressure drop most want one of element, still
It definitely also cannot zero presence in molten iron.It is learnt by multigroup test data, it is 0.15% there are optimum value, when it is reached
During to optimum value, molten iron flow is optimal, and can also normal pressure-off, it is crucial that at 0.15% iron carbon pressure drop
It can reach optimal.
The mass percentage optimum value of sulphur is 0.1%, and main cause is the excessively high mobility that can influence molten iron, according to phase
Pass data shows that variation of the element sulphur in molten iron is extremely complex, and the reaction of series occurs, but passes through test data and test,
Although element sulphur is harmful but also cannot be less than 0.05%, the iron hoop not so cast will not have crackle appearance, seriously affect iron
The pressure-off of ring.
The mass percentage optimum value of nickel element is 0.15%, and nickel plays an important role of graphitizer, and similar with silicon is had
Help carbide decomposition, the nickel element of appropriate level is effective for crystal grain thinning and graphite size, can be suitably and element silicon
It is used cooperatively, reduces pressure drop effect more.
The mass percentage optimum value of rare earth element is 0.4%, and rare earth can play certain desulfidation, Er Qieshi
The value of amount can be to the hypereutectic cast iron mechanical property of carbon equivalent high, and can be very good to reduce iron carbon pressure drop.
In the dedicated hematite iron of aluminium electrolysis anode provided by the invention, carbon equivalent be preferably between 4.18%~4.34% it
Between (according to the content calculation of carbon, silicon, phosphorus).
Second aspect, the present invention provides a kind of preparation method of the dedicated hematite iron of aluminium electrolysis anode, feature exists
In including step：It adds raw materials into intermediate frequency furnace, electrical heating is melted, and when melting to molten iron state, it is clear to carry out first time scum silica frost
Reason；In molten iron after scum silica frost cleans out in first time, iron silicon adjustment ferrosilicon index is added in；Continue to heat using intermediate frequency furnace, directly
It is all melted to ferrosilicon, carries out second of scum silica frost cleaning；After second of scum silica frost cleans out, by molten iron casting, aluminium electroloysis is obtained
The dedicated hematite iron of anode.
Preferably, raw material includes：Mild steel, carburant and ferrosilicon.
Preferably, mild steel comes from waste and old machine iron.
Preferably, after second of scum silica frost cleans out, the temperature of molten iron is 1400~1500 DEG C.
The third aspect, the present invention also protect application of the hematite iron in electrode is prepared.
Preferably, electrode is aluminium electrolysis anode.
Technical solution provided by the invention has following advantageous effect：(1) present invention is by the way that silicone content is heightened, phosphorus
Content is turned down, and adds in suitable rare earth element, controls the content of nickel element, the iron carbon pressure drop for the hematite iron being prepared
It can control in optimum range, the indication range pressure drop that average pressure drop can be than in the prior art is reduced to 25~30mV,
By taking 100,000 tons of electrolytic aluminiums as an example, power consumption cost 3,200,000 or so can be saved every year；(2) aluminium electrolysis anode of the prior art is used
The pig iron index phosphorus content it is excessively high, when in electrolytic cell useization pawl, P elements can be flowed into electrolyte or in aluminium night, shadow
Ring primary aluminum quality and current efficiency；And in hematite iron provided by the invention, phosphorus content is relatively low, ensure molten iron mobility and
During brittleness, can enter to avoid phosphorus element sulphur in cell bath reduces the adverse effect of electrolytic cell currents efficiency, so as to subtract
The risk of few P elements pollution.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
It obtains substantially or is recognized by the practice of the present invention.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described.Implement below
Example is only used for clearly illustrating technical scheme, therefore be intended only as example, and cannot limit this hair with this
Bright protection domain.Experimental method in following embodiments is conventional method unless otherwise specified.Institute in following embodiments
Test material is to be commercially available from regular shops unless otherwise specified.Quantitative test in following embodiment,
Three repeated experiments are set, and data are the average value or mean+SD of three repeated experiments.
The present invention provides a kind of dedicated hematite iron of aluminium electrolysis anode, wherein：
The mass percentage of carbon is 2.3%~3.34%；
The mass percentage of silicon is 3.0%~3.7%；
The mass percentage of manganese is less than 0.8%；
The mass percentage of phosphorus is 0.15%；
The mass percentage of sulphur is 0.051%~0.2%；
The mass percentage of nickel element is 0.1%~1.0%；
The mass percentage of rare earth element is 0.3%~0.5%.
In addition, the present invention also provides a kind of preparation method of the dedicated hematite iron of above-mentioned aluminium electrolysis anode, including
Following steps：
By the pig iron and mild steel (waste and old machine iron) with 4:1 mass ratio is added in intermediate frequency furnace, and electrical heating is melted, and waits to melt extremely
During molten iron state, first time scum silica frost cleaning is carried out；
In molten iron after scum silica frost cleans out in first time, suitable iron silicon adjustment ferrosilicon index is added in；
Continue to heat using intermediate frequency furnace, until ferrosilicon all fusings of vindication, carry out second of scum silica frost cleaning；
After second of scum silica frost cleans out, by the molten iron casting that temperature is 1400~1500 DEG C, it is special to obtain aluminium electrolysis anode
Hematite iron.
The dedicated hematite iron of aluminium electrolysis anode (Innovation Indicator/standard) provided by the invention and aluminium of the prior art electricity
In the pig iron (originally index/professional standard) for solving anode, the mass percentage of each element is as shown in table 1 below.
Table 1 innovates the comparing result of standard and professional standard
| Element | C (%) | Si (%) | Mn (%) | P (%) | S (%) |
| Originally index | 2.6~3.5 | 2.0~3.0 | 0.6~0.9 | 0.8~1.6 | <0.2 |
| Innovation Indicator | 2.3~3.34 | 3.0~3.7 | <0.8 | 0.15 | 0.051~0.2 |
With reference to specific embodiment to dedicated hematite iron of aluminium electrolysis anode provided by the invention and preparation method thereof
It is described further.
Embodiment one
The present embodiment provides a kind of dedicated hematite iron of aluminium electrolysis anode, wherein：
The mass percentage of carbon is 3.20%；
The mass percentage of silicon is 3.20%；
The mass percentage of manganese is 0.35%；
The mass percentage of phosphorus is 0.15%；
The mass percentage of sulphur is 0.1%.
Comparative example one
This comparative example provides a kind of aluminium electrolysis anode with the pig iron (professional standard), wherein：
The mass percentage of carbon is 2.85%；
The mass percentage of silicon is 2.7%；
The mass percentage of manganese is 0.85%；
The mass percentage of phosphorus is 0.15%；
The mass percentage of sulphur is 0.044%.
Comparative example two
This comparative example provides a kind of aluminium electrolysis anode pig iron (phosphorus content exceeds the offline of code test data), wherein：
The mass percentage of carbon is 3.35%；
The mass percentage of silicon is 2.6%；
The mass percentage of manganese is 0.65%；
The mass percentage of phosphorus is 0.09%；
The mass percentage of sulphur is 0.065%.
Comparative example three
This comparative example provides a kind of aluminium electrolysis anode pig iron (phosphorus content is reached the standard grade beyond code test data), wherein：
The mass percentage of carbon is 3.65%；
The mass percentage of silicon is 3.00%；
The mass percentage of manganese is 0.5%；
The mass percentage of phosphorus is 0.20%；
The mass percentage of sulphur is 0.05%.
The pig iron that embodiment one and comparative example one, comparative example two, comparative example three are prepared carries out iron carbon pressure fall-off test,
Obtained result is as shown in table 2 below.The pig iron being prepared according to embodiment one and comparative example one, comparative example two, comparative example three
Test data comparison, it is optimal that the pig iron that embodiment one is prepared can reduce pressure drop data, while molten iron flow, pressure-off
Situation is best.
2 iron carbon pressure of table drop test number compares
Embodiment two
The present embodiment provides a kind of preparation method of the dedicated hematite iron of aluminium electrolysis anode described in embodiment one, including
Following steps：
By the pig iron and mild steel (waste and old machine iron) with 4:1 mass ratio is added in intermediate frequency furnace, and electrical heating is melted, and waits to melt extremely
During molten iron state, first time scum silica frost cleaning is carried out；
In molten iron after scum silica frost cleans out in first time, suitable iron silicon adjustment ferrosilicon index is added in；
Continue to heat using intermediate frequency furnace, until ferrosilicon all fusings of vindication, carry out second of scum silica frost cleaning；
After second of scum silica frost cleans out, by the molten iron casting that temperature is 1450 DEG C, it is dedicated low to obtain aluminium electrolysis anode
The phosphorus pig iron.
It should be noted that unless otherwise indicated, technical term or scientific terminology used in this application should be this hair
The ordinary meaning that bright one of ordinary skill in the art are understood.Unless specifically stated otherwise, otherwise illustrate in these embodiments
Component and opposite step, numerical expression and the numerical value of step are not limit the scope of the invention.It is illustrated and described herein
In all examples, unless otherwise prescribed, any occurrence should be construed as merely illustrative, not as limitation, because
This, other examples of exemplary embodiment can have different values.
In the description of the present invention, it is to be understood that term " first ", " second " are only used for description purpose, and cannot
It is interpreted as indicating or implies relative importance or imply the quantity of the technical characteristic indicated by indicating.Define as a result, " the
One ", one or more this feature can be expressed or be implicitly included to the feature of " second ".In the description of the present invention,
" multiple " are meant that two or more, unless otherwise specifically defined.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution recorded in foregoing embodiments either to which part or all technical characteristic into
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is not made to depart from various embodiments of the present invention technology
The scope of scheme should all cover among protection scope of the present invention.
Claims (10)
1. a kind of dedicated hematite iron of aluminium electrolysis anode, it is characterised in that：
In the hematite iron, the mass percentage of phosphorus is 0.15%.
2. the dedicated hematite iron of aluminium electrolysis anode according to right 1, which is characterized in that in the hematite iron：
The mass percentage of carbon is 2.3%~3.34%；
The mass percentage of silicon is 3.0%~3.7%；
The mass percentage of manganese is less than 0.8%；
The mass percentage of sulphur is 0.051%~0.2%.
3. the dedicated hematite iron of aluminium electrolysis anode according to right 1, which is characterized in that in the hematite iron：
The mass percentage of nickel is 0.1%~1.0%；
The mass percentage of rare earth element is 0.3%~0.5%.
4. the preparation method of the dedicated hematite iron of claim 1-3 any one of them aluminium electrolysis anodes, which is characterized in that bag
Include step：
It adds raw materials into intermediate frequency furnace, electrical heating is melted, and when melting to molten iron state, carries out first time scum silica frost cleaning；
In molten iron after scum silica frost cleans out in first time, iron silicon adjustment ferrosilicon index is added in；
Continue to heat using intermediate frequency furnace, until ferrosilicon all fusings, carry out second of scum silica frost cleaning；
After second of scum silica frost cleans out, by molten iron casting, the dedicated hematite iron of aluminium electrolysis anode is obtained.
5. the preparation method of the dedicated hematite iron of aluminium electrolysis anode according to claim 4, it is characterised in that：
The raw material includes the pig iron and mild steel；The mass ratio of the pig iron and the mild steel is 4:1.
6. the preparation method of the dedicated hematite iron of aluminium electrolysis anode according to claim 4, it is characterised in that：
The raw material includes：Mild steel, carburant and ferrosilicon.
7. the preparation method of the dedicated hematite iron of aluminium electrolysis anode according to claim 5 or 6, it is characterised in that：
The mild steel comes from waste and old machine iron.
8. the preparation method of the dedicated hematite iron of aluminium electrolysis anode according to claim 4, it is characterised in that：
After second of scum silica frost cleans out, the temperature of molten iron is 1400~1500 DEG C.
9. application of the claim 1-3 any one of them hematite irons in electrode is prepared.
10. application according to claim 9, the electrode is aluminium electrolysis anode.
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| CN201711259981.1A CN108048876A (en) | 2017-12-04 | 2017-12-04 | Dedicated hematite iron of aluminium electrolysis anode and preparation method and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443733A (en) * | 2011-12-09 | 2012-05-09 | 云南铝业股份有限公司 | Phosphorus pig iron for improving conducting performance of graphite cathode carbon block |
| CN103205777A (en) * | 2013-04-19 | 2013-07-17 | 扬州润友复合材料有限公司 | Preparation method of rare earth phosphorus pig iron for assembling electrolytic aluminum anode |
| CN103668333A (en) * | 2012-08-31 | 2014-03-26 | 沈阳铝镁设计研究院有限公司 | Low-phosphorous low-sulfur gray pig iron formula for aluminum anode assembly and production method thereof |
-
2017
- 2017-12-04 CN CN201711259981.1A patent/CN108048876A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443733A (en) * | 2011-12-09 | 2012-05-09 | 云南铝业股份有限公司 | Phosphorus pig iron for improving conducting performance of graphite cathode carbon block |
| CN103668333A (en) * | 2012-08-31 | 2014-03-26 | 沈阳铝镁设计研究院有限公司 | Low-phosphorous low-sulfur gray pig iron formula for aluminum anode assembly and production method thereof |
| CN103205777A (en) * | 2013-04-19 | 2013-07-17 | 扬州润友复合材料有限公司 | Preparation method of rare earth phosphorus pig iron for assembling electrolytic aluminum anode |
Non-Patent Citations (1)
| Title |
|---|
| 梁学民等: "《现代铝电解生产技术与管理》", 30 November 2011, 中南大学出版社 * |
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